Organometallic composition for forming a metal alloy pattern and a method of forming such a pattern using the composition

ABSTRACT

An organometallic composition containing an organometallic compound (I) containing Ag, an organometallic compound (II) containing Au, Pd, or Ru, and an organometallic compound (III) containing Ti, Ta, Cr, Mo, Ru, Ni, Pd, Cu, Au, or Al, wherein the metal components of organometallic compounds (II) and (III), respectively, are present in an amount of 0.01˜10 mol % based on the amount of Ag in the organometallic compound (I), and a method of forming a metal alloy pattern using the same. Silver alloy patterns can be obtained through a simplified manufacturing process, which patterns have enhanced heat resistance, adhesiveness and chemical stability. The method may be applied to making a reflective film for LCD and metal wiring (gate, source, drain electrode) for flexible displays or flat panel displays, and further to CMP-free damascene processing and PR-free ITO film deposition.

BACKGROUND OF THE INVENTION

This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2002-73498 filed in Korea on Nov. 25,2002, which is herein incorporated by reference.

1. Field of the Invention

The present invention relates to a composition of organometalliccompounds and to a method of forming a metal alloy pattern using thesame, and more specifically, to a composition of organometalliccompounds comprising organometallic compound (I) containing Ag,organometallic compound (II) containing Au, Pd or Ru, and organometalliccompound (III) containing Ti, Ta, Cr, Mo, Ru, Ni, Pd, Cu, Au or Al,wherein the metal components of the organometallic compounds (II) and(III), respectively, are present in an amount of 0.01˜10 mol % of basedon the amount of Ag in the organometallic compound (I). The presentinvention is also directed to a method of forming a metal alloy patternusing the same.

2. Background of the Invention

In the production of electronic devices such as integrated circuits orliquid crystal displays, microlithography techniques have been used toform a patterned film of materials such as metal, which have desiredelectrical properties, on a certain substrate including a crystallizedsilicon wafer, a glass substrate, and the like. Microlithographycomprises several steps including that of: forming a base layer ofmetallic materials on a substrate through chemical vapor deposition,plasma deposition or electroplating; applying a photoresist layer on themetal layer; exposing the photoresist layer under a photomask to light;developing the photoresist layer to provide a patterned photoresistlayer; and etching the metal layer beneath the patterned photoresistlayer by, for example, reactive etching to provide the metal wiring of amicro-pattern. Such multiple processes of microlithography, in additionto requiring the use of expensive photoresists and chemical etchingmaterial, make it undesirable in the light of cost as well as theprotection of the environment. Moreover, many of the processes should becarried out under high temperatures and/or high pressures, and in suchcondition, diffusion of metallic vapor into the substrate is likely tooccur, resulting in a deterioration of the final electronic devices.Recently, in the field of flexible display and TFT-LCD, demand hasincreased for requiring improved techniques of forming a high qualitygate insulating film and a low resistance source/drain electrode area,and accordingly, diversified studies have been made to provide a moresimplified method of forming a metal pattern.

For example, Japanese Laid-Open Publication No. 62-263973 discloses apatterning method, wherein an electron beam is irradiated on a thin filmof organometallic compounds to form a metal pattern. In this method, anexcessive amount of electron beam is necessary and thus mass-productionof the metal pattern becomes difficult. Also, there is concerns aboutununiformity of the metal pattern.

In U.S. Pat. No. 5,064,685, an ink-containing organometallic compound iscoated on a substrate, and, by exposure to a laser beam, the resultingcoat is allowed to undergo thermal degradation to provide a patternedmetal film. However, this method has a serious shortcoming in that thesubstrate should be subjected to high temperature conditions, andtherefore a pattern of silver or silver alloy cannot be produced by thisprocess.

On the other hand, U.S. Pat. Nos. 5,534,312 and 6,348,239 describe thata metal pattern can be obtained by coating a substrate with anorganometallic complex synthesized by bonding one or more photosensitiveorganic ligands to one or more metal atoms, and exposing the coating toelectromagnetic radiation, wherein any photosensitive resin needs not tobe used. When exposed to electromagnetic radiation, the organometalliccomplex goes through a photochemical reaction, resulting in thedissociation of the organic ligands from the central metal atom. Theremaining metal atoms then react with adjacent metal atoms and/oratmospheric oxygen atoms to form an oxidized metal pattern. However,there are several problems with ligand dissociation throughphotochemical reaction. Typically, the ligand dissociation rate is solow that a large amount of time is required to complete the patterning,and ligand contamination is inevitable. In addition, for improving thereflectivity of the oxidized metal pattern, heat treatment at 200° C. ormore under a mixed gas stream of H₂/N₂ is required, and such treatmentis not applicable to silver and silver alloys.

Thus, there remains a strong demand in the art to develop a method ofproducing a reflective film of silver or silver alloy under mildconditions while improving heat-resistance, adhesiveness and stabilityto discoloration caused by atmospheric oxygen.

At the same time, it should be realized that Silver is difficult to usein the production of a patterned film for numerous reasons: Silver ishighly reactive with non-metallic elements, so it readily becomesdiscolored into a black or milky color, for example, by forming Ag₂S orAgCl with sulfur or chloride in the atmosphere. In addition, silver isvulnerable to heat, so, in the case of producing a reflective film forLCD's by the use of silver, the process temperature should be controlledto prevent diffusion of the outer layer of the silver film. A reflectivefilm comprising silver has a further problem in that yellow, reflectedlight is too strong at short wavelengths (i.e., 450 nm or less), andthis yellowing problem gradually becomes severe. Therefore, silver hasbeen seldom regarded as a useful material in the production of LCD's orPDA's.

In order to overcome these shortcomings of silver, Japanese Laid-OpenPublication Nos. 01-221980 and 01-226765 disclose silver alloyscontaining 0.1˜13.0 wt % of Pt, Pd or Rb and 0.1˜3.0 wt % of at leastone of Cu, Ti, Cr, Ta, Ni, Mo and Al. These alloys, however, areproduced as a film on a substrate by sputtering so that microlithographyprocessing is essential for obtaining a desired pattern, which isproblematic in light of the complexity and expenses as described above.

SUMMARY OF THE INVENTION

One of the features of the present invention is to provide a ternaryorganometallic composition, which includes a first organometalliccompound containing Ag, a second organometallic compound containing atleast one of Au, Pd or Ru, and a third organometallic compoundcontaining at least one of Ti, Ta, Cr, Mo, Ru, Ni, Pd, Cu, Au or Al.

The present invention also defines a method of forming a metal alloypattern using the ternary organometallic composition.

All of the above features and other features of the present inventionwill be successfully achieved as described in the following description.

Further scope of applicability of the present invention will becomeapparent from the detailed description given hereinafter. However, itshould be understood that the detailed description and specificexamples, while indicating preferred embodiments of the invention, aregiven by way of illustration only, since various changes andmodifications within the spirit and scope of the invention will becomeapparent to those skilled in the art from this detailed description.

DETAILED DESCRIPTION OF THE INVENTION

The inventive composition of organometallic compounds as defined by thepresent invention comprises organometallic compound (I) of Formula 1containing Ag, organometallic compound (II) of Formula 2 containing Au,Pd or Ru, and organometallic compound (III) of Formula 3 containing Ti,Ta, Cr, Mo, Ru, Ni, Pd, Cu, Au or Al:Ag_(m)L_(n)X_(p)  Formula 1

-   -   wherein,    -   L is a neutral metallic ligand, which contains 1˜20 carbon atoms        and a donor selected from the group consisting of N, P, O, S and        As;    -   X is an anion selected from the group consisting of F⁻, Cl⁻,        Br⁻, I⁻, alkoxide, hydroxy, cyano(CN⁻), nitro(NO₂ ⁻),        nitrate(NO₃ ⁻), nitroxyl, azide, thiocyanate, isothiocyanate,        tetraalkylborate, tetrahaloborate, hexafluorophosphate(PF₆ ⁻),        triflate(CF₃SO₃ ⁻), tosylate(Ts⁻), sulfate(SO₄ ²⁻),        carbonate(CO₃ ²⁻), carboxylate, diketonate and alkyl anion;    -   m is an integer from 1 to 10;    -   n is an integer from 0 to 40, provided that each L is the same        or different in the case where n is 2 or higher, and provided        that L functions as a ligand connecting Ag atoms in the case        where m is 2 or higher;    -   p is an integer from 0 to 40, provided that each X is the same        or different in the case where p is 2 or higher; and    -   both n and p are not zero at the same time.        M′_(m′)L′_(n′)X′_(p′)  Formula 2    -   wherein,    -   M′ is Au, Pd or Ru;    -   L′ is a neutral ligand containing 1˜20 carbon atoms, which is        selected from the group consisting of amine compounds, phosphine        compounds, phosphite compounds, phosphineoxide compounds, arsine        compounds, thiol compounds, carbonyl compounds, alkenes, alkynes        and arene;    -   X′ is an anion selected from the group consisting of, F⁻, Cl⁻,        Br⁻, I⁻, alkoxide, hydroxy, cyano(CN⁻), nitro(NO₂ ⁻),        nitrate(NO₃ ⁻), nitroxyl, azide, thiocyanate, isothiocyanate,        tetraalkylborate, tetrahaloborate, hexafluorophosphate(PF₆ ⁻),        triflate(CF₃SO₃ ⁻), tosylate(Ts⁻), sulfate(SO₄ ²⁻),        carbonate(CO₃ ²⁻), carboxylate, diketonate and alkyl anion;    -   m′ is an integer from 1 to 10;    -   n′ is an integer from 0 to 40, provided that each L′ is the same        or different in the case where n′ is 2 or higher, and provided        that L′ functions as a ligand connecting metal atoms in the case        where m′ is 2 or higher;    -   p′ is an integer from 0 to 40, provided that each X′ is the same        or different in the case where p′ is 2 or higher; and    -   both p′ and n′ are not zero at the same time; and        M″_(m″)L″_(n″)X″_(p″)  Formula 3    -   wherein,    -   M″ is Ti, Ta, Cr, Mo, Ru(provided that M′ in Formula 2 is not        Ru), Ni, Pd (provided that M′ in Formula 2 is not Pd), Cu, Au        (provided that M′ in Formula 2 is not Au) or Al;    -   L″ is a neutral ligand containing 1˜20 carbon atoms, which is        selected from the group consisting of amine compounds, phosphine        compounds, phosphite compounds, phosphineoxide compounds, arsine        compounds, thiol compounds, carbonyl compounds, alkenes, alkynes        and arene;    -   X″ is an anion selected from the group consisting of F⁻, Cl⁻,        Br⁻, I⁻, alkoxide, hydroxy, cyano(CN⁻), nitro(NO₂ ⁻),        nitrate(NO₃ ⁻), nitroxyl, azide, thiocyanate, isothiocyanate,        tetraalkylborate, tetrahaloborate, hexafluorophosphate(PF₆ ⁻),        triflate(CF₃SO₃ ⁻), tosylate(Ts⁻), sulfate(SO₄ ²⁻),        carbonate(CO₃ ²⁻), carboxylate, diketonate and alkyl anion;    -   m″ is an integer from 1 to 10;    -   n″ is an integer from 0 to 40, provided that each L″ is the same        or different in the case where n″ is 2 or higher, and provided        that L″ functions as a ligand connecting metal atoms in the case        where m″ is 2 or higher; and    -   p″ is an integer from 0 to 40, provided that each X″ is the same        or different in the case where p″ is 2 or higher; and    -   both p″ and n are not zero at the same time.

In the organometallic compounds represented by Formulas 1˜3, the numberof ligand varies according to the kind and oxidation number of the metalatom and it can range from 0 to 6 for every metal atom. The number ofanions can also range from 0 to 6 for every metal atom.

In Formulas 1˜3, each of L, L′ and L″ represents a neutral ligand bondedto metal atom(s) and, independently, is selected from the groupconsisting of amine compounds, phosphine compounds, phosphite compounds,phosphineoxide compounds, arsine compounds, thiol compounds, carbonylcompounds, alkenes, alkynes and arenes.

In Formulas 1˜3, each of X, X′ and X″ represents an anion which makesthe corresponding organometallic compound electrically neutral and mayor may not be coordinated to the metal atom(s).

Preferable examples of the organometallic compound of Formula 1includes, but are not limited to, Ag(NO₂)(PrNH₂)_(n),Ag(NO₃)(PrNH₂)_(n), Ag(NO₂)(BuNH₂)_(n) and Ag(NO₃)(BuNH₂)_(n).Preferable examples of the organometallic compound of formula 2includes, but are not limited to, AuPrNH₂(CN), palladium acetate((CH₃CO₂)₂Pd) and dicarbonylcyclopentadienyl ruthenium(II)dimmer([C₂H₅Ru(CO)₂]₂). Preferable examples of the organometallic compound ofFormula 3 includes, but are not limited to, AuPrNH₂(CN), palladiumacetate ((CH₃CO₂)₂Pd), dicarbonylcyclopentadienyl ruthenium(II)dimmer([C₅H₅Ru(CO)₂]₂), copper(II)₂-ethylhexanoate ([CH₃(CH₂)₃CH(C₂H₅)CO₂]₂Cu)and titanium(IV)isopropoxide (Ti[OCH(CH₃)₂]₄).

In the present invention, the metal component (represented by M′) of thecompound of Formula 2 is different from that (represented by M″) of thecompound of Formula 3.

In the compound of Formula 1, the organic ligand (represented by L) isso sensitive to light that it becomes readily dissociated from thecentral metal atom and is decomposed according to Reaction Formula (i)upon exposure to light. Thus it is possible to obtain a patterned metalfilm without performing the laborious procedure of applying and etchingthe photoresist film as defined in the prior art.

In the present invention, the organometallic compounds of Formulas 2 and3 need not have photosensitivity. Probably, it is believed that theorganometallic compounds of Formulas 2 and 3, being mixed uniformly inthe composition, are captured between the organometallic compound ofFormula 1, and then they decompose during a subsequent annealing processor decompose by being deprived of electrons when the Ag-containingcompound of Formula 1 is reduced upon irradiation. Therefore, in theinventive ternary composition of organometallic compounds, the amount ofthe compounds of Formulas 2 and 3 should be determined based on the Agcontent of the composition. That is, the compounds of Formulas 2 and 3are added to the compound of Formula 1 so that metal components providedby the compounds of Formulas 2 and 3, respectively, are present in anamount of 0.01˜10 mol %, more preferably 0.05˜1 mol % based on the moleamount of Ag provided by the compound of Formula 1. Where the metalcomponent provided by the compound of Formula 2 or 3 exceeds 10 mol %,the results are not satisfactory because the specific resistanceincreases and the photoreaction velocity decreases. On the other hand,where it is less than 0.01 mol %, there is little improvement in theadhesiveness or chemical stability of the final metal alloy pattern.

A method of forming a metal alloy pattern according to the presentinvention comprises the steps of: (i) dissolving the inventivecomposition of organometallic compounds in an organic solvent to producea coating solution; (ii) coating a substrate with the coating solutionto form a coating film; (iii) exposing the coating film to a lightsource using a photomask having a desired pattern; and (iv) developingthe exposed film. As used herein, “metal alloy” is a term that caninclude not only a substantially pure metal alloy but also an oxidethereof.

In step (i), the organic solvent can be exemplified by, but is notlimited to, a nitrile-based solvent such as acetonitrile, propionitrile,pentanenitrile, hexanenitrile, heptanenitrile and isobutylnitrile; analiphatic hydrocarbon solvent such as hexane, heptane, octane anddodecane; an aromatic hydrocarbon solvent such as anisole, mesityleneand xylene; a ketone-based solvent such as methyl isobutyl ketone,1-methyl-2-pyrrolidinone, cyclohexanone and acetone; an ether-basedsolvent such as tetrahydrofuran, diisobutyl ether and isopropyl ether;an acetate-based solvent such as ethyl acetate, butyl acetate andpropylene glycol methyl ether acetate; an alcohol-based solvent such asisopropyl alcohol, butyl alcohol, hexyl alcohol and octyl alcohol; andmixtures thereof.

In step (ii), the substrate can be made of inorganic materials such assilicon and glass; organic materials such as plastic; or compositematerials comprising organic and inorganic matter.

In the present invention, coating of the substrate with the coatingsolution can be accomplished, for example, through spin coating, rollcoating, dip coating, spray coating, flow coating or screen printing,while spin coating is most preferred.

In step (iii), the coating film thus formed is exposed toelectromagnetic radiation. The light source for the electromagneticradiation is not particularly limited, but UV light is most preferred.

During the exposure, the compound of Formula 1, in the unmasked portionof the coating film, undergoes a photochemical reaction as described inReaction Formula (i), resulting in the transformation into a metal alloyor an oxide thereof depending on the atmosphere of the exposure process.More specifically, when the organometallic compound is irradiated, theligand bonded to the metal atom is dissociated and thus adjacentorganometallic compounds become more unstable and consequently areconverted into metal or metal oxide depending on the atmosphere.Although it varies with the type of metals and ligand, generally thephotochemical reaction of organometallic compounds is as follows:through (a) metal to ligand charge transfer; (b) ligand to metal chargetransfer; (c) d-d excite state; or (d) intramolecular charge transfer,whereby the bonds between metals and ligands become unstable and arebroken. And as a result of such photochemical reactions, a solubilitydifference is created between exposed portions and unexposed portions ofthe coating film.

In step (iv), developing is accomplished either with a solvent used forthe preparation of the coating solution in step (i), wherein a singlesolvent or a mixed solvent can be used according to the desireddissolution rate, or with any solvent typically used in semiconductorprocesses, such as tetramethylamoniumhydroxide(TMAH). For the purpose ofimproving clarity of the final pattern, two or more developing solventscan be used alternatively.

In the present invention, the exposure and development steps can beperformed in a vacuum or in an atmosphere of air, O₂, H₂, N₂, Ar or amixed gas thereof. These steps are also performed at room temperature orat a temperature below the thermal decomposition temperature of theorganometallic compounds.

After development, the obtained pattern may undergo a chemical reactionsuch as reduction or oxidation so as to obtain the metal or metal oxide.For obtaining pure metal, reduction is preferred and for obtaining themetal oxide, oxidation is preferred. The reduction or oxidation can beperformed in a vacuum or in an atmosphere of air, O₂, H₂, N₂, Ar or amixed gas thereof. In the reduction step any organic or inorganicreducing agent can be used. Preferable organic reducing agents areexemplified by, but are not limited to, hydrazines, silanes, amines, andderivatives thereof. Preferable inorganic reducing agents can beexemplified by, but are not limited to, metal hydrides such as NaBH₄ andLiAlH₄. These organic and inorganic reducing agents can be usedthemselves or as a solution in a proper solvent, and thus the reductioncan be performed in gas-phase or liquid-phase. Meanwhile, oxidation canbe accomplished by the use of any organic or inorganic oxidant.Non-limiting examples of the organic oxidant include N-oxides such astrimethylamine N-oxide and pyridine N-oxide; peroxides such asbis(trimethylsilyl)peroxide; perbenzoic acid; O₃; and O₂. Inorganicoxidants such as H₂O₂, H₂SO₄ and HNO₃ can also be used.

The inventive method of forming a metal alloy pattern may furthercomprise an annealing step if necessary. Annealing is performed at atemperature of 300° C. or lower, preferably 200° C. or lower, in vacuumor in an atmosphere of air, N₂ gas or a N₂/H₂ mixed gas. In contrastwith the prior art, annealing of the coating film can be accomplished ata relatively low temperature of 300° C. or lower, so a desired metalalloy pattern can be formed even on a heat-labile substrate such asglass or a plastic plate.

According to the present invention, multilayer films of metal alloy canbe obtained which may be employed in most electronic devices. Inmultilayer films, each layer can have the same or different metalcomposition. Such a multilayer film can be obtained by repeating all thesteps of the inventive method of forming a metal alloy pattern,including steps (i) through (iii) and, optionally, the additional stepof reduction, oxidation and/or annealing as described above.

The inventive method of forming a metal alloy pattern may be applied tomaking a reflective film for LCD's and metal wiring (gate, source, drainelectrode) for flexible displays or flat panel displays, and further toCMP-free damascene processing and PR-free ITO film deposition.

The present invention can be more clearly understood with referring tothe following examples. It should be understood that the followingexamples are not intended to restrict the scope of the present inventionin any manner.

Production Examples of Photosensitive Organometallic CoordinationCompounds

Synthesis of Ag(NH₂Pr)_(n)(NO₂) mixture (n=1, 2, 3 and 4)

The synthesis is performed in a N₂ atmosphere while excludingatmospheric moisture and oxygen by Schlenk technique or Glove box. In a50 ml round bottom Schlenk flask, 3.08 g (20.0 mmol) of AgNO₂ isdissolved in 15 ml of acetonitrile (CH₃CN). To this solution is added3.69 g (60.9 mmol) of propylamine in drops using a syringe and theresulting solution is stirred at room temperature for 1 hr. Followingthe stirring, the reaction mixture is filtered through a 0.2 μm membranefilter. With the filtrate shield from light, solvent is completelyevaporated under a reduced pressure for 3˜4 hrs to afford colorless oil.¹H-NMR spectrum is as follows:

¹H-NMR(CD₃OD, ppm): 4.87 [s, 2H, H ₂N—CH₂)], 2.77 [t, 2H, N—CH ₂)], 1.61[m, 2H, CH ₂CH_(3], 1.02) [t, 3H, CH₂CH ₃]

2) Synthesis of Au(NH₂Pr)_(n)(CN) mixture (n=1, 2, 3 and 4)

To a 50 ml round bottom Schlenk flask are added 1.0 g (4.5 mmol) of AuCNand 15 ml of acetonitrile(CH₃CN). To this slurry is added an excessiveamount of propylamine in drops using a syringe and stirred at roomtemperature for 1 hr. Following the stirring, the reaction mixture isfiltered through a 0.2 μm membrane filter. With the filtrate shield fromlight, excessive amine and solvent are completely evaporated under areduced pressure to afford colorless solid matter.

EXAMPLE 1

6.42 g (3.0 mol) of Ag(NH₂Pr)_(n)(NO₂), 0.0013 g (0.0006 mol) ofAu(NH₂Pr)_(n)(CN) (that are produced by production example) and 0.0021 g(0.0006 mol) of copper(II)2-ethylhexanoate are dissolved in 5.4 ml ofacetonitrile to afford a coating solution. This coating solution is thenapplied to a glass substrate by spin coating. Under a photomask, theresulting coating film is exposed to light by using Oriel 200 W UVexposuring system for 10 minutes. Thereafter, the exposed coating filmis developed with acetonitrile to afford a metal alloy pattern. Thispattern is reduced by immersing in 0.05M hydrazine solution, and then itis annealed at 200° C. in vacuum for 2 minutes to afford a finalmetallic reflective film having a certain pattern.

Heat resistance and durability of the reflective film are measured bycomparing decrease of reflectivity after pressure-cooking test. In thistest, at the wavelengths of 480 nm, 633 nm and 700 nm, reflectivities oftest pieces that had been subjected to high-humidity state at 100° C.for 120 minutes are compared with initial values. The results are shownin Table 1 below.

EXAMPLE 2

The procedure of Example 2 is conducted according to the same manner asin the above Example 1, except that palladium(II)acetate was usedinstead of copper(II)2-ethylhexanoate. Heat resistance and durability ofthe reflective film are shown in Table 1 below.

EXAMPLE 3

The procedure of Example 3 is conducted according to the same manner asin the above Example 1, except that titanium (IV) isopropoxide is usedinstead of copper(II)2-ethylhexanoate. Heat resistance and durability ofthe reflective film are shown in Table 1 below.

EXAMPLE 4

The procedure of Example 4 is conducted according to the same manner asin the above Example 1, except that palladium(II)acetate is used insteadof AuCN—(PrNH₂)_(n). Heat resistance and durability of the reflectivefilm are shown in Table 1 below.

EXAMPLE 5

The procedure of Example 5 is conducted according to the same manner asin the above Example 1, except that palladium(II)acetate andtitanium(IV)isopropoxide are used respectively instead ofAuCN—(PrNH₂)_(n) and copper(II)2-ethylhexanoate. Heat resistance anddurability of the reflective film are shown in Table 1 below.

EXAMPLE 6

The procedure of Example 6 is conducted according to the same manner asin the above Example 1, except thatdicarbonylcyclopentadienyl-ruthenium(II) dimmer and AuCN—(PrNH₂)_(n) areused instead of AuCN—(NH₂Pr)_(n) and copper(II)₂-ethylhexanoate. Heatresistance and durability of the reflective film are shown in Table 1below.

EXAMPLE 7

The procedure of Example 7 is conducted according to the same manner asin the above Example 1, except thatdicarbonylcyclopentadienyl-ruthenium(II) dimmer is used instead ofAuCN—(PrNH₂)_(n). Heat resistance and durability of the reflective filmare shown in Table 1 below.

EXAMPLE 8

The procedure of Example 8 is conducted according to the same manner asin the above Example 1, except thatdicarbonylcyclopentadienyl-ruthenium(II) dimmer andtitanium(IV)isopropoxide are used instead of AuCN—(PrNH₂)_(n) andcopper(II)2-ethylhexanoate. Heat resistance and durability of thereflective film are shown in Table 1 below.

COMPARATIVE EXAMPLE 1

In a 10E⁻⁶˜10E⁻¹⁰ Torr vacuum chamber, into which Ar gas is flowing to apressure of 3 mTorr, vapor deposition of Ag by sputtering method isperformed until Ag film having thickness of 300 nm is obtained whilemaintaining a temperature of the substrate at 50° C. Heat resistance anddurability of the reflective film are measured according to the samemanner as in the above Example 1, and the results are shown in Table 1below.

COMPARATIVE EXAMPLE 2

6.42 g (3.0 mol) of Ag(NH₂Pr)_(n)(NO₂) is dissolved in 5.4 ml ofacetonitrile to afford a coating solution. This coating solution is thenapplied to a glass substrate by spin coating. The resulting coating filmis exposed to light using Oriel 200 W UV exposuring system for 10minutes. Thereafter, the exposed coating film is developed withacetonitrile and reduced by immersing in 0.05M hydrazine solution toafford a substantially pure metal alloy film. Subsequently, theprocedure of spin coating through reduction is repeated twice to afforda 3-layer metal alloy film. This 3-layer film is annealed at 200° C. invacuum to afford a final metallic reflective film. Heat resistance anddurability of the reflective film are measured according to the samemanner as in the above Example 1, and the results are shown in Table 1below. TABLE 1 Initial R.I.* Initial Initial Metal (alloy) (480 nm)R.I.* (633 nm) R.I.* (700 nm) film Decrease Decrease Decrease (formingof R.I. of R.I. of R.I. No. method) Used organometallic compound (%) (%)(%) Comp. Ag(sputtering) Ag 245 287 296 Ex. 1 60.4 46.8 42.3 Comp.Ag(SOM**) AgNO₂—(PrNH₂)_(n) 211 270 283 Ex. 2 80.4 77.8 75.9 Ex. 1AgAuCu(SOM) AgNO₂—(PrNH₂)_(n) Au(CN)(PrNH₂)_(n)[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂Cu 212 269 281 13.1 8.5 7.4 Ex. 2 AgAuPd(SOM)AgNO₂—(PrNH₂)_(n) Au(CN)(PrNH₂)_(n) (CH₃CO₂)₂Pd 203 267 279 32.8 35.234.9 Ex. 3 AgAuTi(SOM) AgNO₂—(PrNH₂)_(n) Au(CN)(PrNH₂)_(n)Ti[OCH(CH₃)₂]₄ 90 152 161 21.8 29.8 29.4 Ex. 4 AgPdCu(SOM)AgNO₂—(PrNH₂)_(n) (CH₃CO₂)₂Pd [CH₃(CH₂)₃CH(C₂H₅)CO₂]₂Cu 191 257 272 8.716.9 16.4 Ex. 5 AgPdTi(SOM) AgNO₂—(PrNH₂)_(n) (CH₃CO₂)₂Pd Ti[OCH(CH₃)₂]₄162 236 256 38.5 40.6 40.8 Ex. 6 AgRuAu(SOM) AgNO₂—(PrNH₂)_(n)[C₅H₅Ru(CO)₂]₂ Au(CN)(PrNH₂)_(n) 167 258 272 19.0 29.4 29.4 Ex. 7AgRuCu(SOM) AgNO₂—(PrNH₂)_(n) [C₅H₅Ru(CO)₂]₂ [CH₃(CH₂)₃CH(C₂H₅)CO₂]₂Cu198 261 275 1.9 13.5 13.9 Ex. 8 AgRuTi(SOM) AgNO₂—(PrNH₂)_(n)[C₅H₅Ru(CO)2]2 Ti[OCH(CH₃)₂]₄ 148 249 268 4.3 21.6 22.9*R.I.: reflective index**SOM: spin on metal

As shown in Table 1, although the initial reflectivity of the Agreflective film obtained through sputtering according to Comparativeexample 1 is relatively high, decrease of reflectivity in the pressurecooking test is considerable, implying its poor heat-resistance anddurability. Similarly, the Ag reflective film obtained throughphotoreaction according to Comparative example 2 exhibits high initialreflectivity, but the reflectivity significantly decreases in thepressure cooking test, implying that it is inferior to the inventivereflective films in terms of heat resistance and durability.

These results verify that the reflective films prepared by the use ofthe inventive composition of organometallic compounds have highreflectivity at short wavelength as well as long wavelength and thatthey are so excellent in heat resistance, durability and chemicalstability that they can stand well against high temperature andmoisture.

EXAMPLE 9

6.42 g (3.0 mol) of Ag(NH₂Pr)_(n)(NO₂), 0.0013 g (0.0006 mol) ofAuCN—(PrNH₂)_(n) and 0.0021 g (0.0006 mol) of copper(II)2-ethylhexanoateare dissolved in 5.4 ml of acetonitrile to provide a coating solution.This coating solution is then applied to a glass substrate by spincoating. The resulting coating film is exposed to light using an Oriel200 W UV exposure system for 10 minutes. Thereafter, the exposed coatingfilm is developed with acetonitrile and reduced by immersing in 0.05Mhydrazine solution to afford a substantially pure metal alloy film.Subsequently, the procedure of spin coating through reduction isrepeated twice to afford a 3-layer metal alloy film. This 3-layer filmis annealed at 200° C. in a vacuum to produce a final metallicreflective film. Adhesiveness, specific resistance and reflectivity ofthe reflective film are measured by 3M scotch tape test, 4 point probetest and nano spectrometer, respectively. The results are shown in Table2 in comparison with those of the Ag reflective films obtained fromComparative examples 1 and 2. TABLE 2 Metal Adhesiveness Specific No.(alloy) film (%) resistance(μΩ · cm) Reflective index(700 nm) Comp. Ex.1 Ag(sputter) 100 2.2 296 Comp. Ex. 2 Ag(SOM) 40˜50 7 283 Ex. 9AgAuCu(SOM) 120 15 281

As shown in Table 2, the reflective film made from the inventivecomposition of organometallic compounds is highly improved inadhesiveness, while the decrease in specific resistance and reflectivityis immaterial.

As stated above, by virtue of the present invention, silver alloypatterns can be obtained through a simplified manufacturing process,which patterns have enhanced heat resistance, adhesiveness and chemicalstability. The inventive method may be applied to making a reflectivefilm for LCD and metal wiring (gate, source, drain electrode) forflexible displays or flat panel displays, and further to CMP-freedamascene processing and PR-free ITO film deposition.

Simple modifications and changes of the present invention by personsskilled in the art are considered to be encompassed by the scope of thepresent invention.

1. An organometallic composition comprising organometallic compound (I)of Formula 1 containing Ag, organometallic compound (II) of Formula 2containing at least one of Au, Pd and Ru, and organometallic compound(III) of Formula 3 containing at least one of Ti, Ta, Cr, Mo, Ru, Ni,Pd, Cu, Au and Al, wherein the metal components of organometalliccompounds (II) and (m), respectively, are present in an amount of0.01˜10 mol % based on the mole amount of Ag in the organometalliccompound (I):Ag_(m)L_(n)X_(p)  Formula 1 wherein, L is a neutral metallic ligand,which comprises 1˜20 carbon atoms and a donor selected from the groupconsisting of N, P, O, S and As; X is an anion selected from the groupconsisting of F⁻, Cl⁻, Br⁻, I⁻, alkoxide, hydroxy, cyano(CN⁻), nitro(NO₂⁻), nitrate(NO₃ ⁻), nitroxyl, azide, thiocyanate, isothiocyanate,tetraalkylborate, tetrahaloborate, hexafluorophosphate(PF₆ ⁻),triflate(CF₃SO₃ ⁻), tosylate(Ts⁻), sulfate(SO₄ ²⁻), carbonate(CO₃ ²⁻),carboxylate, diketonate and alkyl anion; m is an integer from 1 to 10; nis an integer from 0 to 40, provided that each L is the same ordifferent in the case where n is 2 or higher, and provided that Lfunctions as a ligand connecting Ag atoms in the case where m is 2 orhigher; p is an integer from 0 to 40, provided that each X is same ordifferent in case that p is 2 or higher; and both n and p are not zeroat the same time;M′_(m′)L′_(n′)X′_(p′)  Formula 2 wherein, M′ is Au, Pd or Ru; L′ is aneutral ligand comprising 1˜20 carbon atoms, which is selected from thegroup consisting of amine compounds, phosphine compounds, phosphitecompounds, phosphineoxide compounds, arsine compounds, thiol compounds,carbonyl compounds, alkenes, alkynes and arene; X′ is an anion selectedfrom the group consisting of, F⁻, Cl⁻, Br⁻, I⁻, alkoxide, hydroxy,cyano(CN⁻), nitro(NO₂ ⁻), nitrate(NO₃ ⁻), nitroxyl, azide, thiocyanate,isothiocyanate, tetraalkylborate, tetrahaloborate,hexafluorophosphate(PF₆ ⁻), triflate(CF₃SO₃ ⁻), tosylate(Ts⁻),sulfate(SO₄ ²⁻), carbonate(CO₃ ²⁻), carboxylate, diketonate and alkylanion; m′is an integer from 1 to 10; n′ is an integer from 0 to 40,provided that each L′ is the same or different in the case where n′ is 2or higher, and provided that L′ functions as a ligand connecting metalatoms in the case where m′ is 2 or higher; p′ is an integer from 0 to40, provided that each X′ is the same or different in the case where p′is 2 or higher; and both p′ and n′ are not zero at the same time; andM″_(m″)L″_(n″)X″_(p″)  Formula 3 wherein, M″ is Ti, Ta, Cr, Mo, Ru(provided that M′ in Formula 2 is not Ru), Ni, Pd (provided that M′ inFormula 2 is not Pd), Cu, Au (provided that M′ in Formula 2 is not Au)or Al; L″ is a neutral ligand comprising 1˜20 carbon atoms, which isselected from the group consisting of amine compounds, phosphinecompounds, phosphite compounds, phosphineoxide compounds, arsinecompounds, thiol compounds, carbonyl compounds, alkenes, alkynes andarenes; X″ is an anion selected from the group consisting of F⁻, Cl⁻,Br⁻, I⁻, alkoxide, hydroxy, cyano(CN⁻), nitro(NO₂ ⁻), nitrate(NO₃ ⁻),nitroxyl, azide, thiocyanate, isothiocyanate, tetraalkylborate,tetrahaloborate, hexafluorophosphate(PF₆ ⁻), triflate(CF₃SO₃ ⁻),tosylate(Ts⁻), sulfate(SO₄ ²⁻), carbonate(CO₃ ²⁻), carboxylate,diketonate and alkyl anion; m″ is an integer from 1 to 10; n″ is aninteger from 0 to 40, provided that each L″ is the same or different inthe case where n″ is 2 or higher, and provided that L″ functions as aligand connecting metal atoms in the case where m″ is 2 or higher; andp″ is an integer from 0 to 40, provided that each X″ is the same ordifferent in the case where p″ is 2 or higher; and both p″ and n are notzero at the same time.
 2. The composition according to claim 1, whereinL represents a neutral ligand selected from the group consisting ofamine compounds, phosphine compounds, phosphite compounds,phosphineoxide compounds, arsine compounds, thiol compounds, carbonylcompounds, alkenes, alkynes and arene.
 3. A method of forming a patternof a metal alloy or oxide thereof, which comprises (i) dissolving theorganometallic composition of claim 1 in an organic solvent to produce acoating solution; (ii) coating a substrate with the coating solution toform a coating film; (iii) exposing the coating film to a light sourceunder a photomask having a desired pattern; and (iv) developing theexposed film.
 4. The method according to claim 3, wherein the coating instep (ii) is accomplished by spin coating, dip coating, spray coating,flow coating or screen printing.
 5. The method of claim 3, wherein theorganic solvent in step (i) is selected from the group consisting of anitrile-based solvent, an aliphatic hydrocarbon solvent, an aromatichydrocarbon solvent, a ketone-based solvent, an ether-based solvent, anacetate-based solvent, an alcohol-based solvent, a silicon-basedsolvent, and mixtures thereof.
 6. The method of claim 3, wherein thelight source in step (iii) is UV light.
 7. The method of claim 3,wherein the steps (iii) and (iv) are accomplished in a vacuum or in anatmosphere of air, O₂, H₂, N₂, Ar or a mixed gas thereof.
 8. The methodaccording to claim 3, further comprising the step of reduction oroxidation and/or the step of annealing.
 9. The method of claim 8,wherein the annealing is accomplished at a temperature of 300° C. orlower in a vacuum or in an atmosphere of air, N₂ gas or a N₂/H₂ mixedgas.
 10. The method according to claim 3, wherein the steps (ii) through(iv) are repeated at least twice to produce a multi-layer pattern ofmetal alloy or oxide thereof.
 11. A pattern of a metal alloy or oxide ofan organometallic composition comprising organometallic compound (I) ofFormula 1 containing Ag, organometallic compound (II) of Formula 2containing at least one of Au, Pd and Ru, and organometallic compound(III) of Formula 3 containing at least one of Ti, Ta, Cr, Mo, Ru, Ni,Pd, Cu, Au and Al, wherein the metal components of organometalliccompounds (II) and (III), respectively, are present in an amount of0.01˜10 mol % based on the mole amount of Ag in the organometalliccompound (I):Ag_(m)L_(n)X_(p)  Formula 1 wherein, L is a neutral metallic ligand,which comprises 1˜20 carbon atoms and a donor selected from the groupconsisting of N, P, O, S and As; X is an anion selected from the groupconsisting of F⁻, Cl⁻, Br⁻, I⁻, alkoxide, hydroxy, cyano(CN⁻), nitro(NO₂⁻), nitrate(NO₃ ⁻), nitroxyl, azide, thiocyanate, isothiocyanate,tetraalkylborate, tetrahaloborate, hexafluorophosphate(PF₆ ⁻),triflate(CF₃SO₃ ⁻), tosylate(Ts⁻), sulfate(SO₄ ²⁻), carbonate(CO₃ ²⁻),carboxylate, diketonate and alkyl anion; m is an integer from 1 to 10; nis an integer from 0 to 40, provided that each L is the same ordifferent in the case where n is 2 or higher, and provided that Lfunctions as a ligand connecting Ag atoms in the case where m is 2 orhigher; p is an integer from 0 to 40, provided that each X is same ordifferent in case that p is 2 or higher; and both n and p are not zeroat the same time;M′_(m′)L′_(n′)X′_(p′)  Formula 2 wherein, M′ is Au, Pd or Ru; L′ is aneutral ligand comprising 1˜20 carbon atoms, which is selected from thegroup consisting of amine compounds, phosphine compounds, phosphitecompounds, phosphineoxide compounds, arsine compounds, thiol compounds,carbonyl compounds, alkenes, alkynes and arene; X′ is an anion selectedfrom the group consisting of, F⁻, Cl⁻, Br⁻, I⁻, alkoxide, hydroxy,cyano(CN⁻), nitro(NO₂ ⁻), nitrate(NO₃ ⁻), nitroxyl, azide, thiocyanate,isothiocyanate, tetraalkylborate, tetrahaloborate,hexafluorophosphate(PF₆ ⁻), triflate(CF₃SO₃ ⁻), tosylate(Ts⁻),sulfate(SO₄ ²⁻), carbonate(CO₃ ²⁻), carboxylate, diketonate and alkylanion; m′ is an integer from 1 to 10; n′ is an integer from 0 to 40,provided that each L′ is the same or different in the case where n′ is 2or higher, and provided that L′ functions as a ligand connecting metalatoms in the case where m′ is 2 or higher; p′ is an integer from 0 to40, provided that each X′ is the same or different in the case where p′is 2 or higher; and both p′ and n′ are not zero at the same time; andM″_(m″)L″_(n″)X″_(p″)  Formula 3 wherein, M″ is Ti, Ta, Cr, Mo, Ru(provided that M′ in Formula 2 is not Ru), Ni, Pd (provided that M′ inFormula 2 is not Pd), Cu, Au (provided that M′ in Formula 2 is not Au)or Al; L″ is a neutral ligand comprising 1˜20 carbon atoms, which isselected from the group consisting of amine compounds, phosphinecompounds, phosphite compounds, phosphineoxide compounds, arsinecompounds, thiol compounds, carbonyl compounds, alkenes, alkynes andarenes; X″ is an anion selected from the group consisting of F⁻, Cl⁻,Br⁻, I⁻, alkoxide, hydroxy, cyano(CN⁻), nitro(NO₂ ⁻), nitrate(NO₃ ⁻),nitroxyl, azide, thiocyanate, isothiocyanate, tetraalkylborate,tetrahaloborate, hexafluorophosphate(PF₆ ⁻), triflate(CF₃SO₃ ⁻),tosylate(Ts⁻), sulfate(SO₄ ²⁻), carbonate(CO₃ ²⁻), carboxylate,diketonate and alkyl anion; m″ is an integer from 1 to 10; n″ is aninteger from 0 to 40, provided that each L″ is the same or different inthe case where n″ is 2 or higher, and provided that L″ functions as aligand connecting metal atoms in the case where m″ is 2 or higher; andp″ is an integer from 0 to 40, provided that each X″ is the same ordifferent in the case where p″ is 2 or higher; and both p″ and n are notzero at the same time.